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Acta Cryst. (2007). E63, m2903    [ doi:10.1107/S1600536807053834 ]

Bis(2-amino-1-benzylpyridinium) bis(2,2-dicyanoethene-1,1-dithiolato-[kappa]2S,S')nickelate(II)

Y. Hou, Q. Huang, H. Zuo and C. Ni

Abstract top

A new [Ni(imnt)2]2- salt (imnt2- is 2,2-dicyanoethene-1,1-dithiolate) with a 1-benzyl-2-aminopyridinium [(Bz2NH2py)+] cation, (C12H13N2)2[Ni(C4N2S2)2], was obtained by the direct reaction of NiCl2·6H2O, K2imnt and (Bz2NH2py)+·Br- in water. The NiII ion lies on an inversion centre and the asymmetric unit contains a (Bz2NH2py)+ cation and one-half of the Ni(imnt)22- anion. The NiII ion adopts a square-planar coordination geometry. In the crystal structure, N-H...N and C-H...N hydrogen bonds are observed between the anions and the cations.

Comment top

Transition metal complexes with 2,2-dicyanoethene-1,1-dithiolate have received much attention in molecular materials research (Liu et al., 1998). In these complexes, the topology and the size of the counterions used with Ni(imnt)22− anions play an important role in tuning the stacks of anions and cations (Liu et al., 1996; Liu et al., 2006; Feng et al., 2007).

The structure of (I) consists of one (Bz2NH2py)+ cation and one-half of a Ni(imnt)2 anion in the asymmetric unit as the NiII ion lies on an inversion centre. The [Bz2NH2py]+ cation adopts a conformation in which both the phenyl ring and pyridine ring are twisted with respect to the C10/C11/N3 plane with dihedral angles of 47.3 (2)° for the phenyl ring, 80.0 (3)° for the pyridine ring, respectively. The phenyl ring and the pyridine ring make a dihedral angle of 102.4 (3)° to one another·The N4 atom deviates from pyridine plane by 0.012 (2) Å. The NiS4 core exhibits a square planar coordination geometry with Ni—S distances 2.2172 (12) and 2.2071 (12) Å respectively, and the S1—Ni1—S2 bond angle within the four-membered ring is 79.16 (4)°. The two N atoms of the CN groups deviate from the Ni1/S1/S2/C1 plane by −0.068 (2) Å for N1 and 0.008 (2) Å for N2.

Four different hydrogen bonds were observed in the crystal structure of (I): C4—H4A···N2, C11—H11B···N2 and C13—H13···N1 (Table 1 and Fig.2).

Related literature top

For the use of Ni(imnt)22− complexes in molecular materials research, see: Liu et al. (1998). For related Ni(imnt)22− complexes with square-planar geometry displaying C—H···N hydrogen bonds, see: Liu et al. (1996, 2006); Feng et al. (2007).

Experimental top

The title compound was prepared by the direct reaction of NiCl2·6H2O, K2imnt and (Bz2NH2py)+Br− in H2O. Red block-like single crystals were obtained by slow evaporation of a CH3CN solution at room temperature over about two weeks.

Refinement top

H atoms bonded to the amine N atom were located in a difference map and refined with distance restraints of N—H = 0.86 (2) Å, and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. Hydrogen atoms have been omitted and labelled atoms are related to unlabelled atoms by the symmetry operation −x, −y,-z + 2.
[Figure 2] Fig. 2. The crystal packing of (I) showing the hydrogen bonds (dashed lines) between the cations and anions.
Bis(2-amino-1-benzylpyridinium) bis(2,2-dicyanoethene-1,1-dithiolato- κ2S,S')nickelate(II) top
Crystal data top
(C12H13N2)2[Ni(C4N2S2)2]F000 = 1464
Mr = 709.56Dx = 1.405 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3342 reflections
a = 20.247 (5) Åθ = 2.4–27.2º
b = 10.764 (3) ŵ = 0.86 mm−1
c = 15.973 (4) ÅT = 291 (2) K
β = 105.462 (3)ºBlock, brown
V = 3355.3 (15) Å30.34 × 0.26 × 0.21 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		1915 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Monochromator: graphiteθmax = 25.1º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −22→24
Tmin = 0.758, Tmax = 0.840k = −12→12
7805 measured reflectionsl = −19→19
2951 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.151  w = 1/[σ2(Fo2) + (0.086P)2 + 1.2P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2951 reflectionsΔρmax = 0.58 e Å−3
205 parametersΔρmin = −0.41 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C12H13N2)2[Ni(C4N2S2)2]V = 3355.3 (15) Å3
Mr = 709.56Z = 4
Monoclinic, C2/cMo Kα
a = 20.247 (5) ŵ = 0.86 mm−1
b = 10.764 (3) ÅT = 291 (2) K
c = 15.973 (4) Å0.34 × 0.26 × 0.21 mm
β = 105.462 (3)º
Data collection top
Bruker SMART APEX CCD
diffractometer		2951 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1915 reflections with I > 2σ(I)
Tmin = 0.758, Tmax = 0.840Rint = 0.034
7805 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046205 parameters
wR(F2) = 0.151H-atom parameters constrained
S = 1.05Δρmax = 0.58 e Å−3
2951 reflectionsΔρmin = −0.41 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.00000.00001.00000.0462 (2)
S10.01956 (5)0.09604 (10)0.88616 (6)0.0525 (3)
S20.11309 (5)0.00334 (9)1.03689 (6)0.0513 (3)
N10.1351 (2)0.2227 (4)0.7590 (3)0.0906 (14)
N20.2833 (2)0.0855 (4)0.9958 (3)0.0938 (14)
N30.03295 (17)0.3881 (3)0.42297 (19)0.0486 (8)
N40.0768 (2)0.5702 (4)0.3819 (3)0.0825 (12)
H4A0.11770.54290.40390.099*
H4B0.07060.64220.35780.099*
C10.10582 (19)0.0789 (3)0.9387 (2)0.0467 (9)
C20.1580 (2)0.1163 (4)0.9074 (3)0.0519 (10)
C30.1461 (2)0.1762 (4)0.8249 (3)0.0623 (11)
C40.2278 (2)0.0997 (4)0.9569 (3)0.0630 (12)
C50.1997 (2)0.3066 (5)0.3907 (3)0.0756 (13)
H50.22520.36260.43090.091*
C60.2293 (3)0.2487 (5)0.3325 (4)0.0922 (17)
H60.27490.26460.33460.111*
C70.1924 (3)0.1688 (5)0.2723 (3)0.0878 (16)
H70.21240.13170.23250.105*
C80.1259 (3)0.1428 (5)0.2702 (3)0.0771 (14)
H80.10070.08760.22920.092*
C90.0963 (2)0.1980 (4)0.3284 (3)0.0623 (11)
H90.05120.17900.32700.075*
C100.1327 (2)0.2820 (4)0.3895 (2)0.0543 (10)
C110.1030 (2)0.3355 (4)0.4583 (2)0.0593 (11)
H11A0.10110.27090.50000.071*
H11B0.13310.40040.48890.071*
C120.0231 (2)0.5009 (4)0.3852 (2)0.0547 (10)
C13−0.0437 (3)0.5437 (5)0.3506 (3)0.0735 (13)
H13−0.05100.62190.32500.088*
C14−0.0978 (3)0.4719 (6)0.3541 (3)0.0826 (16)
H14−0.14230.49950.32960.099*
C15−0.0864 (3)0.3576 (6)0.3943 (4)0.0835 (16)
H15−0.12310.30800.39820.100*
C16−0.0217 (3)0.3186 (4)0.4277 (3)0.0712 (13)
H16−0.01420.24150.45490.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0352 (4)0.0506 (5)0.0526 (4)0.0029 (3)0.0115 (3)−0.0090 (3)
S10.0367 (5)0.0617 (7)0.0573 (6)0.0055 (5)0.0093 (4)−0.0032 (5)
S20.0376 (5)0.0602 (7)0.0537 (6)0.0044 (5)0.0080 (4)−0.0037 (5)
N10.073 (3)0.104 (3)0.103 (3)0.020 (2)0.038 (3)0.037 (3)
N20.043 (2)0.092 (3)0.144 (4)0.008 (2)0.018 (3)0.032 (3)
N30.053 (2)0.0446 (19)0.0499 (17)0.0025 (15)0.0167 (15)0.0033 (14)
N40.070 (3)0.066 (3)0.102 (3)−0.018 (2)0.007 (2)0.021 (2)
C10.041 (2)0.038 (2)0.055 (2)0.0149 (17)0.0029 (17)−0.0129 (17)
C20.043 (2)0.049 (2)0.063 (2)0.0108 (18)0.0128 (19)0.0061 (19)
C30.047 (3)0.056 (3)0.089 (3)0.012 (2)0.029 (2)0.010 (3)
C40.038 (2)0.059 (3)0.095 (3)0.007 (2)0.022 (2)0.015 (2)
C50.061 (3)0.086 (4)0.080 (3)−0.005 (3)0.019 (3)−0.018 (3)
C60.065 (3)0.118 (5)0.102 (4)0.009 (3)0.036 (3)−0.009 (4)
C70.094 (4)0.102 (4)0.073 (3)0.023 (3)0.034 (3)−0.017 (3)
C80.096 (4)0.072 (3)0.065 (3)−0.001 (3)0.024 (3)−0.011 (2)
C90.066 (3)0.058 (3)0.066 (3)−0.001 (2)0.022 (2)0.003 (2)
C100.059 (3)0.050 (2)0.053 (2)0.008 (2)0.013 (2)0.0070 (19)
C110.066 (3)0.056 (3)0.055 (2)0.014 (2)0.013 (2)0.011 (2)
C120.061 (3)0.050 (2)0.049 (2)−0.004 (2)0.0066 (19)0.002 (2)
C130.067 (3)0.067 (3)0.073 (3)0.009 (3)−0.005 (3)0.002 (2)
C140.053 (3)0.105 (5)0.078 (3)0.012 (3)−0.002 (3)−0.031 (3)
C150.061 (3)0.099 (4)0.100 (4)−0.023 (3)0.037 (3)−0.033 (3)
C160.084 (4)0.056 (3)0.088 (3)−0.011 (3)0.048 (3)−0.002 (2)
Geometric parameters (Å, °) top
Ni1—S22.2074 (11)C6—C71.356 (7)
Ni1—S2i2.2074 (11)C6—H60.9300
Ni1—S12.2173 (11)C7—C81.368 (7)
Ni1—S1i2.2173 (11)C7—H70.9300
S1—C11.734 (4)C8—C91.368 (6)
S2—C11.738 (4)C8—H80.9300
N1—C31.133 (5)C9—C101.389 (6)
N2—C41.140 (5)C9—H90.9300
N3—C121.347 (5)C10—C111.502 (6)
N3—C161.356 (5)C11—H11A0.9700
N3—C111.491 (5)C11—H11B0.9700
N4—C121.331 (5)C12—C131.396 (6)
N4—H4A0.8600C13—C141.354 (7)
N4—H4B0.8600C13—H130.9300
C1—C21.345 (6)C14—C151.379 (7)
C2—C31.428 (6)C14—H140.9300
C2—C41.436 (5)C15—C161.342 (7)
C5—C101.377 (6)C15—H150.9300
C5—C61.382 (7)C16—H160.9300
C5—H50.9300
S2—Ni1—S2i180.000 (13)C9—C8—C7120.0 (5)
S2—Ni1—S179.16 (4)C9—C8—H8120.0
S2i—Ni1—S1100.84 (4)C7—C8—H8120.0
S2—Ni1—S1i100.84 (4)C8—C9—C10120.9 (4)
S2i—Ni1—S1i79.16 (4)C8—C9—H9119.5
S1—Ni1—S1i180.0C10—C9—H9119.5
C1—S1—Ni186.03 (14)C5—C10—C9118.1 (4)
C1—S2—Ni186.24 (13)C5—C10—C11120.1 (4)
C12—N3—C16119.8 (4)C9—C10—C11121.5 (4)
C12—N3—C11121.6 (4)N3—C11—C10113.3 (3)
C16—N3—C11118.5 (4)N3—C11—H11A108.9
C12—N4—H4A120.0C10—C11—H11A108.9
C12—N4—H4B120.0N3—C11—H11B108.9
H4A—N4—H4B120.0C10—C11—H11B108.9
C2—C1—S1125.3 (3)H11A—C11—H11B107.7
C2—C1—S2126.1 (3)N4—C12—N3119.9 (4)
S1—C1—S2108.6 (2)N4—C12—C13121.0 (4)
C1—C2—C3121.4 (4)N3—C12—C13119.2 (4)
C1—C2—C4120.9 (4)C14—C13—C12120.3 (5)
C3—C2—C4117.7 (4)C14—C13—H13119.9
N1—C3—C2178.4 (5)C12—C13—H13119.9
N2—C4—C2179.3 (6)C13—C14—C15119.5 (5)
C10—C5—C6120.4 (5)C13—C14—H14120.3
C10—C5—H5119.8C15—C14—H14120.3
C6—C5—H5119.8C16—C15—C14119.3 (5)
C7—C6—C5120.5 (5)C16—C15—H15120.4
C7—C6—H6119.8C14—C15—H15120.4
C5—C6—H6119.8C15—C16—N3122.0 (5)
C6—C7—C8120.0 (5)C15—C16—H16119.0
C6—C7—H7120.0N3—C16—H16119.0
C8—C7—H7120.0
Symmetry codes: (i) −x, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N2ii0.862.252.986 (6)143
C11—H11B···N2ii0.972.583.490 (6)156
C13—H13···N1iii0.932.513.329 (7)148
Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N2i0.862.252.986 (6)143
C11—H11B···N2i0.972.583.490 (6)156
C13—H13···N1ii0.932.513.329 (7)148
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x, −y+1, −z+1.
Acknowledgements top

The authors thank the Science and Technology Project (No. 2007B011000008) from the Guangdong Science and Technology Department and the President's Science Foundation of South China Agricultural University (No. 2005 K092) for financial support.

references
References top

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